Aminoacetonitriles

Reactions were carried out by condensing the o-aminoacetonitrile with carbon oxysulfide in the presence of benzaldehyde or its substituted derivatives, in aicoho) as solvent. 

With secondary alkanolamines, aldehydes in the presence of K CO yield di-tertiary amines, which, on distillation, break down into a,P unsaturated amines and secondary amines. With a mono- or dialkanolamine, an alkaU metal cyanide, and an aldehyde or ketone, aminoacetonitriles are formed. 

Aminoacetonitrile bisulfate [151-63-3] M 154.1, m 188 (dec) Crystd from aqueous EtOH. 

The reaction of a-aminonitriles and carbon disulphide was stated by Cook and Heilbron to give 5-amino-2-mercaptothiazoles however, they later found that the same reaction with aminoacetonitrile was more complex. When aminoacetonitrile sulphate in ethanolic solution was treated with carbon disulphide, the dithiodicarbamate 9 was formed. Benzylation was then carried out treatment of the resulting ester 10 with phosphorus tribromide with subsequent loss of water gave 5-amino-2-benzylthiothiazole 11 in a quantitative fashion. The rapid reaction was thought to be the first example of the formation of a 5-aminothiazole from an a-aminoamide. 

The synthesis of 5-amino-4-carbethoxy-2-benzylthiazole 17 via the reaction of ethyl aminocyanoacetate 15 with methyl dithiophenylacetate 16 provided the first general synthesis of the previously little known 5-aminothiazoles. Similarly, the reaction between aminoacetonitrile 18 and sodium dithiophenylacetate 19 at room temperature gave 5-amino-2-benzylthiazole 20 in excellent yield. 

A solution of sodium methoxide, prepared from sodium (23 g) and dry methanol (500 mL), was added drop-wise at 0 °C to a stirred suspension of aminoacetonitrile hydrochloride (18, 100 g, 1.08 mol) in dry methanol (100 rnL). After stirring for 2 h at rt the precipitated sodium chloride was filtered off and the filtrate concentrated in vacuo. EtOAc (20 mL) was added and evaporated under reduced pressure to remove all traces of methanol. The oily residue was dissolved in dry EtOAc (100 mL) and anhydrous sodium sulfate added. After cooling, the precipitate was filtered off. The solution of crude aminoacetonitrile was used without further purification. This solution was added drop-wise during a period of 1 h to a vigorously stirred, ice-cooled solution of carbon disulphide (100 mL, 1.66 mol) in dry EtOAc (100 mL) under an N2 atmosphere. Continued mechanical stirring and water-free conditions were essential. The mixture was stirred at 0 °C for 1 h. The resultant precipitate was filtered off, washed with EtaO and dried, giving the product 50 as yellow crystals (99 g, 75 % on amount of sodium), m.p. 131 °C dec. IR (KBr) v max 1630, 1500 cm. ... 

Aluminum hydroxide Aluminum nicotinate Aluminum isopropoxide Aceglutamide aluminum Tioclomarol Aminoacetonitrile Octopamine HCI p-Ami noacetophenone Acetohexamide... 

Methyl chloroacetate, 7,17 Methyl cyanoacetate, 3, 56 Methylene Aminoacetonitrile, 4, 31,47... 

C2H4N2 540-61-4) see Estazolam Orotic acid aminoacetonitrile monohydrochloride (C2H5CIN2 6077-/4-9) see Octopamine... 

The related sydnone imine hydrochloride 147 has also been isolated in low yield by treating N-nitroso-A -diphenylphosphinylmethylglycinonitrile 146 with anhydrous HQ and ether at low temperature (2), in a manner similar to that described previously for other nitrosamines of aminoacetonitrile (80). 

The 4(5)-amino-2-substituted imidazoles (45) and (46) have been prepared (50JCS2775) by condensation of aminoacetonitrile (30) with the thio-iminoether hydrochloride salts (40) and (41), respectively. These 4(5)-aminoimidazoles (45, 46) were isolated as their hydrochloride salts in yields of 36 and 90% (Scheme 3). 

Treatment of 4 with glycinonitrile (aminoacetonitrile) affords50,a) (N-cyanomethyl-D-glucofuranosylamine)urono-6,3-lactone. Its negative optical rotation is an indication of the /3-d configuration of this compound. 

The condensation of aldehydes and ketones with aminoacetonitriles, although it requires more vigorous soliddiquid catalytic conditions to produce the cyano-enamines, is preferable in many respects to the traditional Wittig-Horner or Peterson procedures [45]. Hydroxyalkylphosphonates are obtained from the catalysed aldol condensation of nitromethane with acylphosphonates [46]. 

Nitroalkanes react with Jt-deficient alkenes, for example, p-nitro ketones are produced from a,P-unsaturated ketones [41], whereas allylic nitro compounds have been prepared via the Michael-type addition of nitroalkanes with electron-deficient alkynes (Table 6.19). The reaction in either dimethylsulphoxide [42] or dimethyl-formamide [43] is catalysed by potassium fluoride in the presence of benzyltriethyl-ammonium chloride the reaction with dimethyl acetylenedicarboxylate is only successful in dimethylsulphoxide [42], Primary nitroalkanes produce double Michael adducts [42,44], A-Protected a-aminoacetonitriles react with alkynes under catalysed solidiliquid conditions to produce the Michael adducts [45] which, upon treatment with aqueous copper(Il) sulphate, are converted into a,p-unsaturated ketones. 

The total asymmetric syntheses of natural (lS,2S)-norcoronamic 72a and of (lS,2S)-coronamic acid 73 have been obtained from the diastereoselective cyclization of chiral non-racemic 2-(Ar-benzylideneamino)-4-chlorobutyronitriles [98] but one of the shortest syntheses of these attractive amino acids was based on the diastereoselective palladium(0)-catalyzed alkylation and S cyclization of l,4-dichlorobut-2-ene by the anion of 2-aminoacetonitrile derivatives [99]. On the other hand, diastereoselective palladium(0)-catalyzed azidation of chiral non-racemic 1-alkenylcyclopropyl esters provide non-natural (lk,2S)-norcoro-namic acid, enantiomerically pure [100]. 

The syntheses of photochromes in which the heterocycles are separated by the maleimide ring described in the literature were as time-consuming as the syntheses of compounds based on maleic anhydride. A general approach to these photochromes is exemplified in Scheme 55 using unsymmetrical photochrome 180 (98BCJ1101). Here, the treatment of 2-methoxybenzothiophene with oxalyl chloride and aminoacetonitrile... 

The direct reaction of a-hydroxyiminoketones with aminoacetonitriles was found to be a good route to pyrazine derivatives . However, in some cases the yields of products were not high. Recently, it was described that the reaction of oximes 338 with aminoacetonitriles was catalyzed by FeCls. In this case 2-aminopyrazines 339 were obtained in 55-80% yields (equation 147) . ... 

Catalytic hydrogenation of iV-(o-nitrophenyl)aminoacetonitriles 192 with palladium(ll) oxide hydrate gives high yields of quinoxaline A -oxides 193 through condensing the reduced hydroxylamine intermediate with nitrile (Equation 31) <2001EJ0987>. 

Das N-Benzy -N-(trmethylsilyl-methyl)-aminoacetonitril laflt sich durch Reaktion von Benzylamin mit Chlormethyl-trimethyl-silan und nachfolgende Reaktion mit Formalde-hyd und Kaliumcyanid herstellen. 

Aminoacetonitrile hydrochloride [6011-14-9] M 92.5, m 166-167 , 172-174 . Recrystd from dil EtOH hygroscopic leaflets. Best to crystallise from absolute EtOH-Et2O (1 1) and then recryst from absolute EtOH. The m recorded range from 144° to 174°. The free base has b 58°/15mm with partial decomposition. [J Prakt Chem [2] 65 189 1902, JACS 56 2197 1934 JCS 1371 1947]. 

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